EP0327735A1 - Procédé pour modifier un tamis moléculaire - Google Patents

Procédé pour modifier un tamis moléculaire Download PDF

Info

Publication number
EP0327735A1
EP0327735A1 EP88200253A EP88200253A EP0327735A1 EP 0327735 A1 EP0327735 A1 EP 0327735A1 EP 88200253 A EP88200253 A EP 88200253A EP 88200253 A EP88200253 A EP 88200253A EP 0327735 A1 EP0327735 A1 EP 0327735A1
Authority
EP
European Patent Office
Prior art keywords
sample
molecular sieve
modifying agent
process according
adsorption
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP88200253A
Other languages
German (de)
English (en)
Other versions
EP0327735B1 (fr
Inventor
Etienne Vansant
Serge Moreau
Jan Verbiest
Paul De Bièvre
Jos Gislain Leon Philippaerts
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
European Atomic Energy Community Euratom
Original Assignee
European Atomic Energy Community Euratom
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by European Atomic Energy Community Euratom filed Critical European Atomic Energy Community Euratom
Priority to ES88200253T priority Critical patent/ES2077561T3/es
Priority to AT88200253T priority patent/ATE125731T1/de
Priority to DE3854266T priority patent/DE3854266T2/de
Priority to EP88200253A priority patent/EP0327735B1/fr
Priority to US07/308,105 priority patent/US5039641A/en
Priority to PT89667A priority patent/PT89667B/pt
Priority to CA000590769A priority patent/CA1334530C/fr
Priority to DK063689A priority patent/DK63689A/da
Priority to IE43789A priority patent/IE67867B1/en
Priority to JP1033523A priority patent/JP2708212B2/ja
Publication of EP0327735A1 publication Critical patent/EP0327735A1/fr
Application granted granted Critical
Publication of EP0327735B1 publication Critical patent/EP0327735B1/fr
Priority to GR950402311T priority patent/GR3017198T3/el
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
    • B01J20/16—Alumino-silicates
    • B01J20/18—Synthetic zeolitic molecular sieves
    • B01J20/186—Chemical treatments in view of modifying the properties of the sieve, e.g. increasing the stability or the activity, also decreasing the activity
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography

Definitions

  • the invention concerns a process for modifying a molecular sieve, whereby the molecular sieve is brought into contact with a modifying agent.
  • Modification of molecular sieves or zeolites is an important process to obtain products with different properties.
  • both the chemical structure and the pore geometry of the molecular sieve are changed. This has an influence on the kind of molecules that can enter the pores, so that the catalytic properties and the separation characteristics of the molecular sieves are changed.
  • Both the molecular sieving and the adsorption selectivity may be altered by cation exchange or decationi­zation, and/or preadsorption of polar molecules.
  • the pore size and affinity of a molecular sieve can also be altered by a chemical modification of the molecular sieve structure using reactants as X x H y (SiH4 or B2H6).
  • X x H y reactants as X x H y
  • B2H6 reactants as X x H y
  • the free diameters of the zeolitic pores and therefore the molecular sieving properties of a zeolite, and also the electric field and hence the adsorption selectivity are permanently changed.
  • the chemical modification with silane on zeolites Y, mordenite LP and dealuminated mordenite LP changes the intracrystalline free volume and the effective pore size of the zeolites.
  • a chemisorption of diborane alters the sorption characteris­tics of zeolites.
  • the mechanism of both modification procedures can be divided in three parts: the primary chemisorption of the reactant with the zeolite, the secondary reactions inside the channels and the reaction with water of the treated substrate.
  • the effective pore size can be changed, in a controlled way, by applying silanation and/or boranation processes under well-defined reaction conditions, such as degree of chemisorption, reaction temperature and pressure, extent of secondary reactions, reaction time, etc.
  • the known process for modifying molecular sieves has the disadvantage that it involves the use of gaseous reactants, i.e. silane or diborane, which requires very careful and complex processing, in view of the hazards involved in handling these products.
  • the invention thus comprises a process for modifying a molecular sieve, whereby the molecular sieve is brought into contact with a modifying agent containing at least one weak acid, a salt of a weak acid or a derivative of a weak acid of at least one element of Groups III, IV or V of the Periodic Table of Elements, whereafter the resulting mixture is subjected to a thermal treatment.
  • the compounds formed in the channels and cages influence the molecular sieving and the selective adsorption characteristics of the substrates.
  • the resulting sorption behaviour depends on the nature of the introduced obstructions, their location and interaction with the molecular sieve. Therefore a mechanism has been proposed to elucidate the observed adsorption properties in the case of boric acid.
  • boric acid H3BO3
  • the boric acid will polymerise during the thermal treatment to boron-oxides.
  • the metaboric acid undergoes several other transitions resulting in its ⁇ -, ⁇ - or ⁇ -form.
  • the metaboric acid will enter the zeolite and fill the pores and can dimerize
  • the other modifying reagents used are believed to act in a similar way.
  • the molecular sieves are modified by the same manipulations based on a mixing of compounds and a thermal treatment. The high temperatures induce also the formation of different polymerized oxides compounds inside the channels of the molecular sieves. These implanted compounds act as obstructions and change the gas-substrate interactions compared with the original, unmodified sample.
  • the contact between molecular sieve and the modifying agent can preferably be carried out in a number of ways:
  • the molecular sieve that has been brought into contact with the modifying agent (the mixture) is subsequently subjected to a thermal treatment at a temperature of at least 250°C.
  • drying and/or activating step in order to remove free and/or bound solvent, previous to the thermal treatment.
  • This drying and/or activating step can be carried out at reduced pressure, for example to prevent decomposition of organic solvent or to facilitate the removal of solvent. It is not necessary that the steps of drying and/or activating on the one hand and thermal treatment on the other, are clearly distinguishable from each other, for example by intermediate cooling.
  • the temperature is increased to a value above 250°C for a period of time sufficient to obtain the required polymerization of the modifying agent.
  • the time for this ranges from 0,5 to 24 hours or more, whereas the temperature can be between 250°C and 750°C. Shorter times or lower temperatures tend to give in­sufficient results, whereas longer times do not give additional advantages. The same applies to higher tempera­tures, whereby one should be careful to avoid that too much modifying agent becomes gaseous, or that the molecular sieve structure collapses.
  • the molecular sieves to be treated in accordance with the invention can be any natural or synthetic molecular sieve or zeolite.
  • Zeolites and molecular sieves are known in the art and can suitably be defined as product with a crystallized microporous structure, such as crystalline alumino silicates with an Si/Al molar ratio of 1 to 100, preferably 1-20. Examples are mordenite SP and LP, zeolite A, X and Y, ZSM-5, clinoptilolite, ferrieriete, silicalite, erionite, chabazite, etc. in H- or cation form. It is also possible to use a molecular sieve that contains metal species.
  • the modifying agent must be capable of forming polymerized structures in the molecular sieve and is of inorganic nature. These requirements are fullfilled by weak acids of the elements of Group III, IV and V of the Periodic Table, as well as the salts and derivatives thereof. These weak acids usually have the structure H a E b O c , wherein H and 0 stand for hydrogen and oxygen respectively, and E is the said element. a, b and c are such that the structure is neutral. Salts thereof, such as with Na, K, Ca, Al, NH3, etc. can also be used.
  • the modifying agent is chosen from the group of boric acid, silicic acid, acids of phosphor and salts thereof, more in particular it is H3BO3, NaH2PO2, Na4P2O7.10H2O, K3PO4, (NH4)2HPO2, Na2B4O7.10H2O and Si(OH)4. It is also possible to use derivatives of the weak acids, such as acid halides.
  • the amount of modifying agent can vary within wide ranges and is mainly determined by the degree of modification that is required. Preferred ranges of the weight ratio of molecular sieve to modifying agent are between 100 : 1 and 1 : 1, more in particular 10 : 1 to 3 : 1. These ratio applies to the amount of molecular sieve and the amount of dry modifying agent, not taking into account any liquid that can be used in the process. The amount of liquid is of influence on the results obtained.
  • the ratio of liquid (if used) to modifying agent ranges from 400 : 1 tot 1 : 20.
  • the modified molecular sieve can be used for various purposes. It is possible to apply it as a catalyst for chemical reactions, optionally after the outer surface has been made inert. Another application is the separation or storage of gases.
  • the modified molecular sieves can also be used as selective ion exchangers in liquids, or to purify liquids.
  • Fig. 1 shows the adsorption kinetics of Xe at 0°C.
  • Fig. 3 shows the adsorption kinetics of Xe at 0°C. A relatively high adsorption is observed for Xe. 3 grams of the parent sample (particle size ⁇ 150 ⁇ m) were mixed with 10 ml of a colloidal solution of silicic acid in methanol. The slurry was dried at 100°C and heated for 3 hours at 400°C in air. The sample was dehydrated and tested with the test gases. Fig. 3 shows a decrease of the adsorption capacity for Xe at 0°C due to the implanted obstructions inside the cages of the Y-type zeolite.
  • Fig. 6 shows a the observed sorption characteristics for Xe at 0°C. No equilibrium was observed after 25 min. 3 g of the parent sample (fraction ⁇ 150 ⁇ m) were mixed with 0.15 g boric acid powder and stirred with 3 ml H2O at room temperature. Afterwards, the sample was thermally treated for 1 hour at 105°C and for 2 hours at 400°C, both in air. 2 g of this sample were dehydrated overnight at 454°C in vacuum to study the adsorption kinetics of Xe. Fig. 6 shows a capacity decrease.
  • Fig. 8 shows the adsorption kinetics of N2 at 0°C indicating a fast adsorption rate A. 4 g of the parent sample (particle size > 800 ⁇ m) were treated with 20 ml of a 4% boric acid solution and the water was evaporated at 70°C. The dried sample was heated for 2 hours at 500°C in air. 2 g of this sample were outgassed overnight at 450°C. The adsorption kinetics shown on Fig. 9 indicate slow diffusion-controlled adsorption for N2.
  • Example 8 same as Example 8.
  • 2 g of the parent (particle size 250-800 ⁇ m) were treated with 10 ml of a 4% boric acid solution and the water was evaporated at 70°C.
  • the dried sample was heated for 2 hours at 500°C in air. This sample was outgassed overnight at 453°C.
  • the adsorption kinetics shown in Fig. 9, indicate diffusion-controlled adsorption for N2 at 0°C.
  • Example 8 same as Example 8. C. 5 g of the parent sample (particle size ⁇ 150 ⁇ m) were treated with 25 ml of a 4% boric acid solution and the water was evaporated at 70°C. The dried sample was heated for 2 hours at 500°C in air. 2 g of this sample were outgassed overnight at 428°C. Comparing the kinetics of N2 with Example 9 the uptake N2 is decreased. A higher modification can be obtained when the particle size is small.
  • Fig. 12 shows that the adsorption of Xe is not only decreased in capacity but one observes also a diffusion-controlled adsorption caused by the boron-oxygen compounds blocking the zeolite pores.
  • the parent sample used in this experiment is E127 NaM 543 (SCGP). Its sorption characteristics for Xe and Kr are shown in Fig. 13. 5 g (fraction 250-800 ⁇ m) were treated with 25 ml of a 4% Na4P2O7.10H2O solution by evaporating the water at 90°C. The sample was afterwards heated for two hours at 500°C in air.
  • Fig. 13 shows the kinetic run of Kr at 0°C on this modified sample. Kr has a strong diffusion-controlled sorption kinetic run.
  • the parent sample used in this example was E127NaM 543 treated with an aqueous KNO3 solution.
  • the Na+-ions were exchanged for K+-ions using 100 g KNO3 and 50 g sample E127 in 0.5 l of H2O for 1 night at room temperature.
  • the parent sample used in this example is E127NaM 543 (SCGP) as in Example 22. Its sorption characteristics for Kr are shown in Fig. 16.
  • Fig. 16 shows the diffusion-controlled adsorption of Kr.
  • the parent sample used in this example was CaM CM782 (SCGF; extrudates).
  • Fig. 19 shows a decrease in the adsorption of CH4 at 0°C after modification.
  • the parent sample used in this experiment was CaM CM782 (SCGP; extrudates).
  • Fig. 20 shows the sorption kinetics of Xe at 0°C.
  • 3 g CaM CM782 (fraction ⁇ a 150 ⁇ m) were treated for 1 hour and 30 min at 90°C in a H3BO3-solution (0.15 g H3BO3 in 40 ml H2O). After cooling to room temperature the residual solution was decanted and the sample was dried at 60°C in air. The dried material was thermally treated for 2 hours at 400°C in air.
  • the modified sample shows a decrease in the adsorption capacity at 0°C.
  • Fig. 25 shows the observed sorption characteristics for Xe, Kr, Ar, N2 and 02 at 0°C. After 16 min Xe is still adsorbing.
  • Fig. 26 shows the observed sorption characteristics for Xe at 0°C. After 16 min Xe is still adsorbing.
  • Fig. 26 shows the obtained adsorption behaviour. A capacity decrease occurs with diffusion-controlled adsorption for Xe. The pore-narrowing of this sample is not so effective as the one in Example 26 although the same amount of boric acid was used.
EP88200253A 1988-02-11 1988-02-11 Procédé pour modifier un tamis moléculaire Expired - Lifetime EP0327735B1 (fr)

Priority Applications (11)

Application Number Priority Date Filing Date Title
ES88200253T ES2077561T3 (es) 1988-02-11 1988-02-11 Proceso para la modificacion de un tamiz molecular.
AT88200253T ATE125731T1 (de) 1988-02-11 1988-02-11 Verfahren zur modifizierung eines molekularsiebes.
DE3854266T DE3854266T2 (de) 1988-02-11 1988-02-11 Verfahren zur Modifizierung eines Molekularsiebes.
EP88200253A EP0327735B1 (fr) 1988-02-11 1988-02-11 Procédé pour modifier un tamis moléculaire
US07/308,105 US5039641A (en) 1988-02-11 1989-02-08 Process for modification of a molecular sieve
PT89667A PT89667B (pt) 1988-02-11 1989-02-09 Processo para a modificacao de um crivo molecular
CA000590769A CA1334530C (fr) 1988-02-11 1989-02-10 Procede pour la modification d'un tamis moleculaire
DK063689A DK63689A (da) 1988-02-11 1989-02-10 Fremgangsmaade til modificering af en molekylesigte
IE43789A IE67867B1 (en) 1988-02-11 1989-02-10 Process for modification of a molecular sieve
JP1033523A JP2708212B2 (ja) 1988-02-11 1989-02-13 モレキユラーシーブの改質方法
GR950402311T GR3017198T3 (en) 1988-02-11 1995-08-23 Process for modification of a molecular sieve.

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP88200253A EP0327735B1 (fr) 1988-02-11 1988-02-11 Procédé pour modifier un tamis moléculaire

Publications (2)

Publication Number Publication Date
EP0327735A1 true EP0327735A1 (fr) 1989-08-16
EP0327735B1 EP0327735B1 (fr) 1995-08-02

Family

ID=8199750

Family Applications (1)

Application Number Title Priority Date Filing Date
EP88200253A Expired - Lifetime EP0327735B1 (fr) 1988-02-11 1988-02-11 Procédé pour modifier un tamis moléculaire

Country Status (11)

Country Link
US (1) US5039641A (fr)
EP (1) EP0327735B1 (fr)
JP (1) JP2708212B2 (fr)
AT (1) ATE125731T1 (fr)
CA (1) CA1334530C (fr)
DE (1) DE3854266T2 (fr)
DK (1) DK63689A (fr)
ES (1) ES2077561T3 (fr)
GR (1) GR3017198T3 (fr)
IE (1) IE67867B1 (fr)
PT (1) PT89667B (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1997015528A1 (fr) * 1995-10-24 1997-05-01 The Dow Chemical Company Procede de modification de la porosite d'aluminosilicates et de silices et composes mesoporeux en derivant
US5900226A (en) * 1997-04-09 1999-05-04 Uop Llc Drying agents for non-foamed polyurethanes
US6051647A (en) * 1997-04-09 2000-04-18 Uop Llc Drying agents for non-foamed polyurethanes
FR3033714A1 (fr) * 2015-03-17 2016-09-23 Ceca Sa Adsorbants a faible reactivite pour le sechage de gaz et/ou de liquides

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ES2156481B1 (es) * 1998-03-03 2002-02-01 Univ Valencia Politecnica Procedimiento de obtencion de tamices moleculares inorganicos modificados y su uso como emisores de semioquimicos.
US7078364B2 (en) * 2001-04-20 2006-07-18 University Of Southern California Ship-in-a-bottle catalysts
CN103121663A (zh) * 2011-11-18 2013-05-29 扬光绿能股份有限公司 氢气产生设备
SG11201503035XA (en) 2012-12-06 2015-05-28 Exxonmobil Res & Eng Co Gas separation method using ddr type zeolites with stabilized adsorption activity

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2143340A1 (fr) * 1971-06-24 1973-02-02 Grace W R Ltd
EP0173507A2 (fr) * 1984-08-31 1986-03-05 Mobil Oil Corporation Modification de zéolithes

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3382187A (en) * 1963-10-29 1968-05-07 Union Carbide Corp Wet attrition-resistant molecular sieve bodies and their manufacture
US3377295A (en) * 1964-12-17 1968-04-09 Grace W R & Co Process for making high strength molecular sieve nodules and extrudates
US3326818A (en) * 1965-06-15 1967-06-20 Exxon Research Engineering Co Catalyst composition of a crystalline aluminosilicate and a binder
NL8005645A (nl) * 1980-10-13 1982-05-03 Euratom Werkwijze voor het omkeerbaar opsluiten van gassen of dampen in een natuurlijk of synthetisch zeoliet.
JPS5768144A (en) * 1980-10-15 1982-04-26 Ube Ind Ltd Catalyst for synthesizing styrene
US4377485A (en) * 1981-09-15 1983-03-22 Lenox Institute For Research, Inc. Apparatus and method for clarification of water using combined flotation and filtration processes
US4454241A (en) * 1982-05-24 1984-06-12 Exxon Research And Engineering Co. Phosphorus-containing catalyst
SU1152930A1 (ru) * 1983-11-11 1985-04-30 Белорусский Ордена Трудового Красного Знамени Технологический Институт Им.С.М.Кирова Способ получени фосфорсодержащего цеолита типа @ @
SU1234359A1 (ru) * 1984-12-24 1986-05-30 Белорусский Ордена Трудового Красного Знамени Технологический Институт Им.С.М.Кирова Способ получени кристаллического борофосфата цеолитной структуры

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2143340A1 (fr) * 1971-06-24 1973-02-02 Grace W R Ltd
EP0173507A2 (fr) * 1984-08-31 1986-03-05 Mobil Oil Corporation Modification de zéolithes

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1997015528A1 (fr) * 1995-10-24 1997-05-01 The Dow Chemical Company Procede de modification de la porosite d'aluminosilicates et de silices et composes mesoporeux en derivant
AU711249B2 (en) * 1995-10-24 1999-10-07 Dow Chemical Company, The Process of modifying the porosity of aluminosilicates and silicas, and mesoporous compositions derived therefrom
US6017508A (en) * 1995-10-24 2000-01-25 The Dow Chemical Company Process of modifying the porosity of aluminosilicates and silicas, and mesoporous compositions derived therefrom
CN1089725C (zh) * 1995-10-24 2002-08-28 陶氏化学公司 改变硅铝酸盐和二氧化硅孔隙度的方法和由该方法制备的中孔率组合物
US5900226A (en) * 1997-04-09 1999-05-04 Uop Llc Drying agents for non-foamed polyurethanes
US6051647A (en) * 1997-04-09 2000-04-18 Uop Llc Drying agents for non-foamed polyurethanes
FR3033714A1 (fr) * 2015-03-17 2016-09-23 Ceca Sa Adsorbants a faible reactivite pour le sechage de gaz et/ou de liquides

Also Published As

Publication number Publication date
DK63689A (da) 1989-08-12
JP2708212B2 (ja) 1998-02-04
IE67867B1 (en) 1996-05-01
ATE125731T1 (de) 1995-08-15
CA1334530C (fr) 1995-02-21
PT89667B (pt) 1994-02-28
DK63689D0 (da) 1989-02-10
US5039641A (en) 1991-08-13
DE3854266T2 (de) 1996-02-15
IE890437L (en) 1989-08-11
DE3854266D1 (de) 1995-09-07
PT89667A (pt) 1989-10-04
GR3017198T3 (en) 1995-11-30
JPH026845A (ja) 1990-01-11
EP0327735B1 (fr) 1995-08-02
ES2077561T3 (es) 1995-12-01

Similar Documents

Publication Publication Date Title
Ng et al. Nanoporous materials with enhanced hydrophilicity and high water sorption capacity
CA1207305A (fr) Synthese de la zeolite zsm-22 a l'aide d'un compose organique heterocyclique
US5527981A (en) Sorption separation with MCM-58
US5417957A (en) Divalent cation exchanged lithium X-zeolite for nitrogen adsorption
KR100351717B1 (ko) 합성다공성결정성mcm-58,그의합성방밥및용도
EP0002079A1 (fr) Silicates crystallins et leurs méthodes de préparation
US3597155A (en) Crystalline mm and process for manufacture thereof
US5032152A (en) Gas separation
EP0327735B1 (fr) Procédé pour modifier un tamis moléculaire
Suzuki et al. Zeolite synthesis in the system pyrrolidine-Na2O Al2O3 SiO2 H2O
Chauvin et al. Dealumination of faujasite, mazzite, and offretite with ammonium hexafluorosilicate
US3513108A (en) Hydrothermally stable catalyst and method for its preparation
JPS6350286B2 (fr)
EP0136068B1 (fr) Zéolithe ZSM-12 à acidité prescrite
CA1204718A (fr) Zeolite
Bolton Molecular sieve zeolites
CA2148773C (fr) Separation de gaz a l'aide de metallosilicates zsm-2 renfermant du lithium
EP0191212B1 (fr) Modification de zéolites avec du fluorure d'ammonium
Flank et al. Perspectives in molecular sieve science
EP0146390B1 (fr) Silicophosphoaluminate cristallin
Tamer Synthesis and characterization of zeolite Beta
US3634533A (en) Method for dehydrating moisture-containing materials using carbon monoxide and a crystalline aluminosilicate catalyst
CA1251439A (fr) Borosilicate cristallin, sa synthese, et son emploi en conversion organique
NZ209129A (en) Synthesising crystalline siliceous molecular sieve material
KR102556628B1 (ko) 높은 실리카 골격조성을 갖는 kfi형 제올라이트 및 그 제조방법, 이를 이용한 프로필렌의 선택적 분리 방법

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE CH DE ES FR GB GR IT LI LU NL SE

17P Request for examination filed

Effective date: 19890929

17Q First examination report despatched

Effective date: 19900924

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE CH DE ES FR GB GR IT LI LU NL SE

REF Corresponds to:

Ref document number: 125731

Country of ref document: AT

Date of ref document: 19950815

Kind code of ref document: T

REF Corresponds to:

Ref document number: 3854266

Country of ref document: DE

Date of ref document: 19950907

ITF It: translation for a ep patent filed

Owner name: STUDIO TORTA SOCIETA' SEMPLICE

REG Reference to a national code

Ref country code: GR

Ref legal event code: FG4A

Free format text: 3017198

ET Fr: translation filed
REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2077561

Country of ref document: ES

Kind code of ref document: T3

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed
PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 19971212

Year of fee payment: 11

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GR

Payment date: 19971216

Year of fee payment: 11

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: AT

Payment date: 19971230

Year of fee payment: 11

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: BE

Payment date: 19980114

Year of fee payment: 11

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: SE

Payment date: 19980115

Year of fee payment: 11

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: LU

Payment date: 19980126

Year of fee payment: 11

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: ES

Payment date: 19980210

Year of fee payment: 11

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: CH

Payment date: 19980216

Year of fee payment: 11

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 19980227

Year of fee payment: 11

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 19980228

Year of fee payment: 11

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 19980316

Year of fee payment: 11

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19990211

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19990211

Ref country code: AT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19990211

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19990212

Ref country code: ES

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19990212

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19990228

Ref country code: GR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19990228

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19990228

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19990228

BERE Be: lapsed

Owner name: EUROPEAN ATOMIC ENERGY COMMUNITY EURATOM

Effective date: 19990228

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19990901

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 19990211

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19991029

EUG Se: european patent has lapsed

Ref document number: 88200253.8

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19991201

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 20010910

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES;WARNING: LAPSES OF ITALIAN PATENTS WITH EFFECTIVE DATE BEFORE 2007 MAY HAVE OCCURRED AT ANY TIME BEFORE 2007. THE CORRECT EFFECTIVE DATE MAY BE DIFFERENT FROM THE ONE RECORDED.

Effective date: 20050211